U.S. patent application number 16/966938 was filed with the patent office on 2021-02-18 for nanoparticles of encapsulated light-absorbing agent, preparation thereof and ophthalmic lens comprising said nanoparticles.
The applicant listed for this patent is ESSILOR INTERNATIONAL. Invention is credited to Pierre FROMENTIN, Tipparat LERTWATTANASERI, Waranya PHOMPAN.
Application Number | 20210048559 16/966938 |
Document ID | / |
Family ID | 1000005208848 |
Filed Date | 2021-02-18 |
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United States Patent
Application |
20210048559 |
Kind Code |
A1 |
FROMENTIN; Pierre ; et
al. |
February 18, 2021 |
Nanoparticles of Encapsulated Light-Absorbing Agent, Preparation
Thereof and Ophthalmic Lens Comprising Said Nanoparticles
Abstract
The invention relates to nanoparticles of a composite material
comprising a light absorbing agent dispersed in a matrix of a
mineral oxide, to a method for the preparation of such
nanoparticles, to the use of said method to modify the hue of
nanoparticles of composite material comprising a light absorbing
agent, and to an ophthalmic lens comprising such nanoparticles.
Inventors: |
FROMENTIN; Pierre; (Bangkok,
TH) ; LERTWATTANASERI; Tipparat; (Bangkok, TH)
; PHOMPAN; Waranya; (Bangkok, TH) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
ESSILOR INTERNATIONAL |
Charenton-le-Pont |
|
FR |
|
|
Family ID: |
1000005208848 |
Appl. No.: |
16/966938 |
Filed: |
February 9, 2018 |
PCT Filed: |
February 9, 2018 |
PCT NO: |
PCT/IB2018/000175 |
371 Date: |
August 3, 2020 |
Current U.S.
Class: |
1/1 |
Current CPC
Class: |
G02B 5/223 20130101;
G02B 1/043 20130101 |
International
Class: |
G02B 1/04 20060101
G02B001/04; G02B 5/22 20060101 G02B005/22 |
Claims
1. Nanoparticles of a composite material comprising at least one
light absorbing agent LA dispersed in a matrix of a mineral oxide,
wherein: the light absorbing agent LA is dispersed in said matrix
in both a monomeric form LA.sub.m and an aggregated form LA.sub.A,
said light absorbing agent LA has an absorbance ratio
A=A.sub.A/A.sub.M ranging from 1.25 to 10, where A.sub.A is
absorbance of LA measured at the wavelength of maximum absorption
of LA.sub.A and A.sub.M is absorbance of LA measured at the
wavelength of maximum absorption of LA.sub.M.
2. The nanoparticles of claim 1, wherein the mineral oxide is
selected from the group comprising silicon dioxide, titanium oxide
and zirconium oxide.
3. The nanoparticles of claim 1, wherein the light absorbing agent
LA.sub.A is an aggregate of at least 2 light absorbing agents
LA.sub.M.
4. The nanoparticles according to claim 1, wherein said light
absorbing agent LA is selected from the group comprising,
phenazines, phenoxazines, phenothiazine, porphyrins, and mixtures
thereof.
5. The nanoparticles according to claim 4, wherein said light
absorbing agent LA is a blue light absorbing agent selected from
the group comprising methylene blue and Nile blue.
6. The nanoparticles according to claim 1, wherein the mineral
oxide of the matrix is SiO.sub.2 and the light absorbing agent LA
is methylene blue.
7. The nanoparticles according to claim 1, wherein said absorbance
ratio A ranges from 1.3 to 5.
8. The nanoparticles according to claim 1, wherein said
nanoparticles have a mean size ranging from 5 nm to 5000 nm.
9. The nanoparticles according to claim 1, wherein the amount of
said absorbing agent ranges from 0.001 to 10 wt. %, relative to the
total weight of said nanoparticles.
10. A method for the preparation of nanoparticles as defined in
claim 1, wherein said method comprises at least the following
steps, i) a step of preparing nanoparticles of a composite material
comprising at least one light absorbing agent in a monomeric form
LA.sub.M dispersed in a matrix of a mineral oxide, ii) a step of
annealing the nanoparticles obtained in step i) at a temperature
ranging from 80 to 300.degree. C. for a period of time ranging from
5 min to 120 hours.
11. The method of claim 10, wherein the step of annealing is
carried out at a temperature ranging from 80 to 180.degree. C. for
30 min to 24 hours.
12. The use of the method as defined in claim 10, further defined
as a method of modifying a hue of nanoparticules of a composite
material comprising at least one light absorbing agent LA dispersed
in a matrix of a mineral oxide.
13. An ophthalmic lens comprising nanoparticles as defined in claim
1.
14. The ophthalmic lens of claim 13, wherein said nanoparticles are
dispersed in a polymer matrix.
15. The ophthalmic lens of claim 14, wherein the amount of said
nanoparticles in the polymer matrix is .ltoreq.1000 ppm.
16. The ophthalmic lens of claim 15, wherein the amount of said
nanoparticles in the polymer matrix is .ltoreq. than 250 ppm.
17. The nanoparticles according to claim 8, wherein said
nanoparticles have a mean size ranging from 100 to 200 nm.
18. The nanoparticles according to claim 9, wherein the amount of
said absorbing agent ranges from 0.1 to 3 wt. %, relative to the
total weight of said nanoparticles.
Description
TECHNICAL FIELD
[0001] The present invention relates to the field of ophthalmic
lenses. More particularly, the invention relates to nanoparticles
of a composite material comprising a light absorbing agent
dispersed in a matrix of a mineral oxide, to a method for the
preparation of such nanoparticles, to the use of said method to
modify the hue of nanoparticles of composite material comprising a
light absorbing agent, and to an ophthalmic lens comprising such
nanoparticles.
BACKGROUND OF THE INVENTION
[0002] Plastic ophthalmic lenses are well known and have a common
usage. Today there are two main categories of plastic lenses, the
first wherein plastic represents a thermoplastic polymer, and the
second wherein plastic represents a thermoset polymer resulting
from the polymerization of a polymerizable composition comprising
monomer and/or oligomer which are able to polymerize under
activation to form a polymer. Among polymers used to manufacture
plastic ophthalmic lenses, mention may be made in particular of
polycarbonates such as for example allyl diglycol carbonate (also
named CR-39). The use of these polymers leads to ophthalmic lenses
having excellent properties in terms safety, cost and ease of
production and optical quality. Although exhibiting such good
properties, plastic ophthalmic lenses have often the drawback of
being slightly colored, in particular yellow colored because the
polymers used for their preparation are themselves slightly
colored, in particular slightly yellow, which results in
unaesthetic effects for the lens wearer.
[0003] One of the solutions known to suppress this unaesthetic
color in ophthalmic lenses is the incorporation of colored
molecules, in particular blue dyes, into the bulk liquid raw
polymerizable formulation (i.e. before polymerization) used during
the manufacturing process to balance the intrinsic and undesired
colour of the polymers and get a final lens which is less colored
or uncolored. However, the molecules used for this purpose are not
always compatible with the bulk liquid raw polymerizable
formulation and they might be degraded during the polymerization
process.
[0004] Patents such as EP2282713, EP2263788 and JP3347140 describe
UV absorbers encapsulated in mineral matrixes for cosmetic
applications to provide protection against sunburns. However, the
high amount of UV-absorbers contained in the nanoparticles and in
the cosmetic composition is not compatible with a liquid
polymerizable composition for the preparation of an ophthalmic
lens. The technology used in these patents is therefore not
directly transposable in the field of ophthalmic lenses.
[0005] In addition, if encapsulation can be a very attractive
technology to compatibilize unstable molecules in a given polymer
formulation, the encapsulation process may also lead to some
changes in the dye spectral properties while comparing to standard
dyes spectra in solution, because of possible interaction with the
mineral matrixes or other factors. It results from these changes
that it is not easy to predict which will be the spectral
properties of the encapsulated dye and if the incorporation of such
encapsulated dye into a bulk liquid polymerizable formulation will
be convenient to balance the intrinsic undesired colour of the lens
polymer matrix.
[0006] There is thus a need for coloured material that can be used
during the manufacturing process of plastic ophthalmic lenses and
the colour of which can be tuned to balance the intrinsic and
undesired color of the lens polymers and get a final lens which is
less colored or uncolored.
[0007] The Applicant has found that this need could be met by using
nanoparticles encapsulating a light absorbing agent having the
property of exhibiting different aggregation states.
SUMMURY OF THE INVENTION
[0008] A first object of the present invention is therefore
nanoparticles of a composite material comprising at least one light
absorbing agent LA dispersed in a matrix of a mineral oxide,
wherein:
[0009] the light absorbing agent LA is dispersed in said matrix in
both a monomeric form LA.sub.m and an aggregated form LA.sub.A,
[0010] said light absorbing agent LA has an absorbance ratio
A=A.sub.A/A.sub.M ranging from 1.25 to 10, where A.sub.A is
absorbance of LA measured at the wavelength of maximum absorption
of LA.sub.A and A.sub.M is absorbance of LA measured at the
wavelength of maximum absorption of LA.sub.M.
[0011] A second object of the present invention is a method for the
preparation of nanoparticles as defined according to the first
object of the present invention, wherein said method comprises at
least the following steps,
[0012] i) a step of preparing nanoparticles of a composite material
comprising at least one light absorbing agent in a monomeric form
LA.sub.M dispersed in a matrix of a mineral oxide,
[0013] ii) a step of annealing the nanoparticles obtained in step
i) at a temperature ranging from 80 to 300.degree. C. for a period
of time ranging from 5 min to 120 hours.
[0014] A third object of the present invention is the use of the
method as defined according to the second object of the present
invention, to modify the hue of nanoparticules of a composite
material comprising at least one light absorbing agent LA dispersed
in a matrix of a mineral oxide.
[0015] Finally, a forth object of the present invention is an
ophthalmic lens comprising nanoparticles as defined according to
the first object of the present invention.
[0016] Thanks to the present invention, the hue of the
nanoparticles can be adjusted by varying the absorbance ratio A to
obtain a color balancing agent which will lead to an ophthalmic
lens with a residual colour as neutral as possible.
[0017] In particular, thanks to the annealing step of the method
according to the invention, a single dye material encapsulated in a
matrix of mineral oxide can thus lead to several hues within a
given interval depending on the process condition, i.e. the
temperature and duration of the annealing step, thus, enabling the
use of the same basic material for different product applications.
In particular, the annealing step is performed to modulate the
aggregation levels of the light absorbing agents that are
responsible for the final color of the nanoparticles.
[0018] Encapsulating the light-absorbing agent has also other
advantages. Mineral particles are a good encapsulation material for
water-soluble light-absorbing agent. Indeed, these particles
present a good compatibility with aprotic mediums such as monomer.
Surface modification enables these particles to be compatible with
most media. This allows using water-soluble light-absorbing agents
in hydrophobic solvents or matrix.
[0019] In addition, nanoparticles can be considered as a
standardization agent: whatever the light absorbing agent
encapsulated, the external surface of nanoparticle interacting with
the monomer can be the same, thus enabling the easy introduction of
a given light-absorbing agent in a formulation if a similar
substrate has already been introduced in a formulation, even with a
different light-absorbing additive.
DETAILED DESCRIPTION
[0020] In a preferred embodiment, the mineral oxide comprised in
the nanoparticles is a transparent material. In particular, the
mineral oxide is preferably selected from the group comprising
silicon dioxide (SiO.sub.2), titanium oxide (TiO.sub.2), zirconium
oxide (ZrO.sub.2) and mixtures thereof. Among these oxides, silicon
dioxide is particularly preferred.
[0021] According to a preferred embodiment, the nanoparticles have
a homogeneous composition from inside to outside in which the light
absorbing agent is uniformly distributed. This feature allows an
acute control on the optical properties of the overall
nanoparticles. According to this feature, the light-absorbing agent
is encapsulated in nanoparticles, i.e. the light-absorbing agent is
contained within or grafted on said nanoparticles.
[0022] In another embodiment, the nanoparticles have a core
containing the light-absorbing additive and a shell surrounding the
core. The shell is preferably chosen so as to isolate the core from
the matrix. As such, the nature of the shell will preferably be
linked to the matrix in which the corresponding particle is meant
to be used.
[0023] Nanoparticles behave like reservoirs, in which
light-absorbing agents are stored and protected. Light-absorbing
agents may be homogenously dispersed in nanoparticles or localized
in the core of nanoparticles. Light-absorbing agents may also be
localized at the surface or inside the porosity of
nanoparticles.
[0024] Indeed, active reactants from the lens composition according
to the invention, i.e. radicals involved in radical polymerization,
will not be able to diffuse in the internal part of nanoparticles.
If light-absorbing additives are located on the surface or in
porosity of nanoparticles, active reactants may reach them, but as
mobility of grafted or trapped additives is hindered, probability
of reaction is lowered and additives are also protected.
[0025] The refractive index of the nanoparticles is preferably from
1.47 to 1.74, as measured according to the ISO 489:1999. More
preferably the refractive index of the nanoparticles is identical
to the refractive index of the polymer matrix. Indeed, the closer
both refractive indices are, the lesser the impact of the
nanoparticles on the overall transmission of the lens
composition.
[0026] The refractive index of mineral-based nanoparticles depends
on the type of mineral oxide or mixture of mineral oxides that is
used to prepare the nanoparticle. As such, the refractive index of
a SiO.sub.2 nanoparticle is 1.47-1.5 and the refractive index of a
nanoparticle comprising a mixture of SiO.sub.2 and TiO.sub.2, a
mixture of SiO.sub.2 and ZrO.sub.2, or a mixture of SiO.sub.2 and
Al.sub.2O.sub.3 can reach 1.56 or 1.6.
[0027] According to the invention, the light absorbing agent LA is
chosen from a colorant, such a dye or a pigment, which can have
several aggregation levels.
[0028] In the sense of the present invention, the light absorbing
agent LA absorbs light in the visible range, from 380 nm to 780 nm.
The light absorbing agent may also have a maximum of absorption in
Ultra Violet range, below 380 nm, but still having a significant
absorption in visible range. The light absorbing agent may also
have a maximum of absorption in Near Infra Red range, above 780 nm,
but still having a significant absorption in visible range.
Preferably maxima of absorption of the light absorbing agent LA are
included in the visible range.
[0029] In the sense of the present invention, a colorant which has
several aggregation levels is a colorant which can be either in
monomeric form (LA.sub.M), or in the form of aggregates (LA.sub.A)
of at least two monomers stacked together by mean of intermolecular
interactions, in particular via Pi-stacking (also called .pi.-.pi.
stacking).
[0030] Preferably, the light absorbing agent LA.sub.A is an
aggregate of at least 2 light absorbing agents LA.sub.M.
[0031] The absorbance ratio A of the light absorbing agent LA
comprised in the composite material of the nanoparticles is the
ratio of the absorbance of LA measured at the wavelength of maximum
absorption of LA.sub.A and A.sub.M is absorbance of LA measured at
the wavelength of maximum absorption of LA.sub.M. This ratio
directly reflects the respective proportions of monomeric form and
aggregated form of the light absorbing agent LA comprised in the
composite material of the nanoparticles.
[0032] According to the invention, the absorbance measurement
protocol consists in dispersing 0.03 wt. % of dried nanoparticles
in a solvent, in particular in the liquid raw monomer used for the
preparation of an ophthalmic lens, such as CR-39, and measuring
absorbance with a UV-Vis spectrophotometer (Cary), with reference
to a blank made of solvent without particles in a 2 mm thick
cuvette. As mentioned above, two absorbance measurements are made,
one at the wavelength of maximum absorption of LA.sub.A to get
A.sub.A and one at the wavelength of maximum absorption of LA.sub.M
to get A.sub.M.
[0033] The light absorbing agent LA is preferably selected from the
group comprising, phenazines, phenoxazines, phenothiazine,
porphyrins, and mixtures thereof. Among these particular light
absorbing agents, blue dyes such as for example methylene blue and
Nile blue are particularly preferred.
[0034] According to a particular and preferred embodiment of the
present invention, the mineral oxide of the matrix is SiO.sub.2 and
the light absorbing agent LA is methylene blue.
[0035] The absorbance ratio A of the light absorbing agent LA
preferably ranges from about 1.3 to 5.
[0036] The amount of the light absorbing agent LA preferably ranges
from about 0.001 to about 10 wt. %, and more preferably from about
0.1 to about 3 wt. %, relative to the total weight of said
nanoparticles.
[0037] In the context of the present invention, the term
"nanoparticles" is intended to mean individualized particles of any
shape having a size, measured in its longest direction, in the
range of about 1 nm to about 10 .mu.m, preferably in the range of
about 5 nm to about 5000 nm, and even more preferably from about
100 to about 200 nm, as measured by the Dynamic Light Scattering
method disclosed herein.
[0038] The nanoparticles according to the present invention
preferably have a spherical form.
[0039] A second object of the present invention is a method for the
preparation of nanoparticles as defined according to the first
object of the present invention, wherein said method comprises at
least the following steps,
[0040] i) a step of preparing nanoparticles of a composite material
comprising at least one light absorbing agent in a monomeric form
LA.sub.M dispersed in a matrix of a mineral oxide,
[0041] ii) a step of annealing the nanoparticles obtained in step
i) at a temperature ranging from 80 to 300.degree. C. for a period
of time ranging from 5 min to 120 hours.
[0042] Nanoparticles of a composite material comprising at least
one light absorbing agent in a monomeric form LA.sub.M dispersed in
a matrix of a mineral oxide of step i) can be prepared by several
methods well known in the art, in particular, by Stober synthesis
or reverse microemulsion.
[0043] As a first example, when the mineral oxide is silicon
dioxide, silica nanoparticles can be prepared by Stober synthesis
by mixing silicon dioxide precursor, such as tetraethyl
orthosilicate, and the light-absorbing agent in an excess of water
containing a low molar-mass alcohol such as ethanol and ammonia. In
the Stober approach, the light-absorbing agent may be
functionalized so as to be able to establish a covalent link with
silica, for example silylated with a conventional silane,
preferably an alkoxysilane. Stober synthesis advantageously yields
monodisperse SiO.sub.2 particles of controllable size.
[0044] As a second example, nanoparticles containing a
light-absorbing agent can also be prepared by reverse
(water-in-oil) microemulsion by mixing an oil phase, such as
cyclohexane and n-hexanol; water; a surfactant such as Triton
X-100; a light absorbing agent, one or more mineral oxide
precursors such as tetraethyl orthosilicate and titanium
alkoxylate; and a pH adjusting agent such as sodium hydroxide. In
the reverse micro-emulsion approach, a larger quantity of polar
light-absorbing agent can be encapsulated in the mineral oxide
matrix than those encapsulated with the Stober synthesis: the
encapsulation yield can be very high, thus avoiding the waste of
expensive light-absorbing agent. Moreover, this method
advantageously allows an easy control of particle size, especially
in the case of reverse microemulsions. Additionally, this method
enables the addition of TiO.sub.2 or ZrO.sub.2 in the silica
nanoparticles.
[0045] Nanoparticles obtained by Stober synthesis and reverse
(water-in-oil) microemulsion are highly reticulated and coated with
hydrophobic silica groups thus preventing leakage of the
light-adsorbing agent out of the nanoparticles and preventing the
migration of a radical inside the nanoparticles during
polymerization of the lens.
[0046] Nanoparticles obtained by the above-detailed method can be
directly engaged into step ii), or firstly pre-treated to reduce
their size, for example with a grinding step.
[0047] According to a preferred embodiment of the present
invention, the step of annealing is carried out at a temperature
ranging from 80 to 180.degree. C. for 30 min to 24 hours.
[0048] The annealing step ii) can be performed for example in an
air oven.
[0049] The annealing step ii) can be carried only once or
alternatively at least 2 times or more to adjust the light
absorbance ratio A if necessary. In that case, the method according
to the invention can comprise a further step iii) of measuring the
absorbance ratio A of said nanoparticules to determine if said
ratio has the desired value or not and if a further step ii) of
annealing is needed or not.
[0050] In particular, thanks to the annealing step of the method
according to the invention, a single dye material encapsulated in a
matrix of mineral oxide can lead to several hues within a given
interval depending on the process condition, i.e. the temperature
and duration of the annealing step, thus, enabling the use of the
same basic material for different product applications. In
particular, the annealing step is performed to modulate the
aggregation levels of the light absorbing agent that are
responsible for the final color of the nanoparticles.
[0051] Therefore, a third object of the present invention is the
use of the method defined according to the second object of the
present invention to modify the hue of nanoparticles of a composite
material comprising at least one light absorbing agent LA dispersed
in a matrix of a mineral oxide.
[0052] The nanoparticles defined according the first object of the
present invention can advantageously be used to balance the
intrinsic and undesired natural color of polymers used to
manufacture ophthalmic lens, in particular to balance the yellow
color.
[0053] The yellowness index (YI) of the cured ophthalmic lens can
be calculated from tristimulus values (X, Y, Z) according to ASTM
D-1925 standard, through the relation: YI=(128 X-106 Z)/Y.
[0054] A forth object of the present invention is thus an
ophthalmic lens comprising nanoparticles as defined according to
the first object of the present invention or prepared according to
the second object of the present invention.
[0055] The ophthalmic lens of the invention comprises a polymer
matrix and nanoparticles which are dispersed therein.
[0056] The polymer matrix is obtained by polymerization of a
polymerizable liquid composition comprising monomer or oligomer in
presence of a catalyst for initiating the polymerization of said
monomer or oligomer.
[0057] The polymer matrix and the nanoparticles dispersed therein
thus form together a composite substrate, i.e. a composite material
having two main surfaces corresponding in the final ophthalmic lens
to the front and rear faces thereof.
[0058] In one embodiment, the ophthalmic lens consists essentially
in the polymer matrix and the nanoparticles dispersed therein.
[0059] In another embodiment, the ophthalmic lens comprises an
optical substrate on which a coating of the polymer matrix and the
nanoparticles dispersed therein is deposited.
[0060] The polymer matrix is preferably a transparent matrix.
[0061] The polymer matrix can be advantageously chosen from a
thermoplastic resin, such as a polyamide, polyimide, polysulfone,
polycarbonate, polyethylene terephthalate,
poly(methyl(meth)acrylate), cellulose triacetate or copolymers
thereof, or is chosen from a thermosetting resin, such as a cyclic
olefin copolymer, a homopolymer or copolymer of allyl esters, a
homopolymer or copolymer of allyl carbonates of linear or branched
aliphatic or aromatic polyols, a homopolymer or copolymer of
(meth)acrylic acid and esters thereof, a homopolymer or copolymer
of thio(meth)acrylic acid and esters thereof, a homopolymer or
copolymer of urethane and thiourethane, a homopolymer or copolymer
of epoxy, a homopolymer or copolymer of sulphide, a homopolymer or
copolymer of disulphide, a homopolymer or copolymer of episulfide,
a homopolymer or copolymer of thiol and isocyanate, and
combinations thereof.
[0062] The amount of said nanoparticles in the polymer matrix can
be .ltoreq.1000 ppm, preferably, .ltoreq. than 250 ppm.
[0063] The polymerizable liquid composition used for generating the
aforesaid polymer matrix--hereinafter referred to as "the
polymerizable composition"--comprises a monomer or oligomer, a
catalyst, and nanoparticles containing a light-absorbing additive
as defined according to the first object of the present invention.
Said monomer or oligomer can be either an allyl or a non-allyl
compound.
[0064] The monomer or oligomer can in particular be an allyl
monomer or an allyl oligomer, i.e. the monomer or the oligomer
included in the polymerizable composition according to the present
invention is a compound comprising an allyl group.
[0065] Examples of suitable allyl compounds include diethylene
glycol bis(allyl carbonate), ethylene glycol bis(allyl carbonate),
oligomers of diethylene glycol bis(allyl carbonate), oligomers of
ethylene glycol bis(allyl carbonate), bisphenol A bis(allyl
carbonate), diallylphthalates such as diallyl phthalate, diallyl
isophthalate and diallyl terephthalate, and mixtures thereof.
[0066] The monomer or the oligomer included in the polymerizable
composition according to the present invention can also be chosen
among non-allyl monomers or oligomers. Examples of suitable
non-allyl compounds include thermosetting materials known as
acrylic monomers having acrylic or methacrylic groups.
(Meth)acrylates may be monofunctional (meth)acrylates or
multifunctional (meth)acrylates bearing from 2 to 6 (meth)acrylic
groups or mixtures thereof. Without limitation, (meth)acrylate
monomers are selected from:
[0067] alkyl (meth)acrylates, in particular (meth)acrylates derived
from adamantine, norbornene, isobornene, cyclopentadiene or
dicyclopentadiene; C.sub.1-C.sub.4 alkyl (meth)acrylates such as
methyl (meth)acrylate and ethyl (meth)acrylate;
[0068] aromatic (meth)acrylates such as benzyl (meth)acrylate,
phenoxy (meth)acrylates or fluorene (meth)acrylates;
[0069] (meth)acrylates derived from bisphenol, especially
bisphenol-A;
[0070] polyalkoxylated aromatic (meth)acrylates such as
polyethoxylated bisphenolate di(meth)acrylates, polyethoxylated
phenol (meth)acrylates;
[0071] polythio(meth)acrylates;
[0072] product of esterification of alkyl (meth)acrylic acids with
polyols or epoxies; and
[0073] mixtures thereof.
[0074] (Meth)acrylates may be further functionalized, especially
with halogen substituents, epoxy, thioepoxy, hydroxyl, thiol,
sulphide, carbonate, urethane or isocyanate function.
[0075] Other examples of suitable non-allyl compounds include
thermosetting materials used to prepare polyurethane or
polythiourethane matrix, i.e. mixture of monomer or oligomer having
at least two isocyanate functions with monomer or oligomer having
at least two alcohol, thiol or epithio functions.
[0076] Monomer or oligomer having at least two isocyanate functions
may be selected from symmetric aromatic diisocyanates such as 2,2'
Methylene diphenyl diisocyanate (2,2' MDI), 4,4' dibenzyl
diisocyanate (4,4' DBDI), 2,6 toluene diisocyanate (2,6 TDI),
xylylene diisocyanate (XDI), 4,4' Methylene diphenyl diisocyanate
(4,4' MDI) or asymmetric aromatic diisocyanates such as 2,4'
Methylene diphenyl diisocyanate (2,4' MDI), 2,4' dibenzyl
diisocyanate (2,4' DBDI), 2,4 toluene diisocyanate (2,4 TDI) or
alicyclic diisocyanates such as Isophorone diisocyanate (IPDI),
2,5(or 2,6)-bis(iso-cyanatomethyl)-Bicyclo[2.2.1]heptane (NDI) or
4,4' Diisocyanato-methylenedicyclohexane (H12MDI) or aliphatic
diisocyanates such as hexamethylene diisocyanate (HDI) or mixtures
thereof.
[0077] Monomer or oligomer having at least two thiol functions may
be selected from Pentaerythritol tetrakis mercaptopropionate,
Pentaerythritol tetrakis mercaptoacetate,
4-Mercaptomethyl-3,6-dithia-1,8-octanedithiol,
4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane, 2,5-d
imercaptomethyl-1,4-dithiane,
2,5-bis[(2-mercaptoethyl)thiomethyl]-1,4-dithiane, 4,8-d
imercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 4,7-d
imercaptomethyl-1,11-dimercapto-3,6,9-trithiaudecane,
5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane and
mixture thereof.
[0078] Monomer or oligomer having at least two epithio functions
may be selected from bis(2,3-epithiopropyl)sulfide,
bis(2,3-epithiopropyl)disulfide,
bis[4-(beta-epithiopropylthio)phenyl]sulfide and
bis[4-(beta-epithiopropyloxy)cyclohexyl]sulfide.
[0079] The polymerizable liquid composition used for generating the
aforesaid matrix comprises:
[0080] a) at least one monomer or oligomer,
[0081] b) at least one catalyst for initiating the polymerization
of said monomer or oligomer,
[0082] c) nanoparticles of a composite material comprising at least
one light absorbing agent LA dispersed in a matrix of a mineral
oxide as defined according to the first object of the present
invention, said nanoparticles being dispersed in said monomer or
oligomer.
[0083] If the monomer or oligomer is of allyl type, the amount of
said allyl monomer or oligomer in the polymerizable composition
used for generating the polymer matrix according to the present
invention may be from 20 to 99% by weight, in particular from 50 to
99% by weight, more particularly from 80 to 98% by weight, even
more particularly from 90 to 97% by weight, based on the total
weight of the composition. In particular, the polymerizable
composition used for generating the polymer matrix may comprise
from 20 to 99% by weight, in particular 50 to 99% by weight, more
particularly from 80 to 98% by weight, even more particularly from
90 to 97% by weight, based on the total weight of the composition,
of diethylene glycol bis(allyl carbonate), oligomers of diethylene
glycol bis(allyl carbonate) or mixtures thereof.
[0084] According to a particular embodiment, the catalyst is
diisopropyl peroxydicarbonate (IPP).
[0085] The amount of catalyst in the polymerizable composition
according to the present invention may be from 1.0 to 5.0% by
weight, in particular from 2.5 to 4.5% by weight, more particularly
from 3.0 to 4.0% by weight, based on the total weight of the
composition.
[0086] The polymerizable composition used for generating the
polymer matrix may also comprise a second monomer or oligomer that
is capable of polymerizing with the allyl monomer or oligomer
described above. Examples of a suitable second monomer include:
aromatic vinyl compounds such as styrene, [alpha]-methylstyrene,
vinyltoluene, chlorostyrene, chloromethylstyrene and
divinylbenzene; alkyl mono(meth)acrylates such as methyl
(meth)acrylate, n-butyl (meth)acrylate, n-hexyl (meth)acrylate,
cyclohexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate,
methoxydiethylene glycol (meth)acrylate, methoxypolyethylene glycol
(meth)acrylate, 3-chloro-2-hydroxypropyl (meth)acrylate, stearyl
(meth)acrylate, lauryl (meth)acrylate, phenyl (meth)acrylate,
glycidyl (meth)acrylate and benzyl (meth)acrylate, 2-hyd roxyethyl
(meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl
(meth)acrylate, 3-phenoxy-2-hydroxypropyl (meth)acrylate and
4-hydroxybutyl (meth)acrylate; di(meth)acrylates such as ethylene
glycol di(meth)acrylate, diethylene glycol di(meth)acrylate,
triethylene glycol di(meth)acrylate, polyethylene glycol
di(meth)acrylate, 1,3-butylene glycol di(meth)acrylate,
1,6-hexanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate,
polypropylene glycol di(meth)acrylate,
2-hydroxy-1,3-di(meth)acryloxypropane,
2,2-bis[4-((meth)acryloxyethoxy)phenyl]propane,
2,2-bis[4-((meth)acryloxydiethoxy)phenyl]propane and
2,2-bis[4-((meth)-acryloxypolyethoxy)phenyl]propane;
tri(meth)acrylates such as trimethylolpropane tri(meth)acrylate and
tetramethylolmethane tri(meth)acrylate; tetra(meth)acrylates such
as tetramethylolmethane tetra(meth)acrylate. These monomers may be
used singly or in combination of two or more. In the above
description, "(meth)acrylate" means "methacrylate" or "acrylate",
and "(meth)acryloxy" means "methacryloxy" or "acryloxy".
[0087] The amount of the second monomer or oligomer in the
polymerizable composition used for generating the polymer matrix
according to the present invention may be from 1 to 80% by weight,
in particular from 1 to 50% by weight, more particularly from 2 to
20% by weight, even more particularly from 3 to 10% by weight,
based on the total weight of the composition.
[0088] If the monomer or oligomer is of (meth)acrylic type, the
amount of said (meth)acrylic monomer or oligomer in the
polymerizable composition used for generating the polymer matrix
according to the present invention is from 20 to 99%, in particular
from 50 to 99% by weight, more particularly from 80 to 98%, even
more particularly from 90 to 97% by weight, based on the total
weight of the composition.
[0089] Examples of monomer of (meth)acrylic are alkyl
mono(meth)acrylates, di(meth)acrylates, tri(meth)acrylates or
tetra(meth)acrylates, as defined above. These monomers may be used
singly or in combination of two or more.
[0090] The polymerizable composition used for generating the
polymer matrix may also comprise a second monomer or oligomer that
is capable of polymerizing with the (meth)acrylic monomer or
oligomer described above.
[0091] Examples of a suitable second monomer include: aromatic
vinyl compounds such as styrene. These monomers may be used singly
or in combination of two or more.
[0092] The amount of the second monomer or oligomer in the
polymerizable composition used for generating the matrix according
to the present invention may be from 1 to 80% by weight, in
particular from 1 to 50% by weight, more particularly from 2 to 20%
by weight, even more particularly from 3 to 10% by weight, based on
the total weight of the composition.
[0093] If the polymer matrix according to the invention is of
polyurethane or polythiourethane type, the monomer or oligomer
having at least two isocyanate functions and monomer or oligomer
having at least two alcohol, thiol or epithio functions are
preferably selected in a stoichiometric ratio, so as to obtain a
complete reaction of all polymerizable functions.
[0094] The catalyst included in the polymerizable liquid
composition according to the present invention is a catalyst that
is suitable for initiating the monomer polymerization, such as for
example an organic peroxide, an organic azo compound, an organotin
compound, and mixtures thereof.
[0095] Examples of a suitable organic peroxide include dialkyl
peroxides, such as diisopropyl peroxide and di-t-butyl peroxide;
ketone peroxides such as methyl ethyl ketone peroxide, methyl
isopropyl ketone peroxide, acetylacetone peroxide, methyl isobutyl
ketone peroxide and cyclohexane peroxide; peroxydicarbonates such
as diisopropyl peroxydicarbonate, bis(4-t-butylcyclohexyl)
peroxydicarbonate, di-sec-butyl peroxydicarbonate and
isopropyl-sec-butylperoxydicarbonate; peroxyesters such as t-butyl
peroxy-2-ethylhexanoate and t-hexyl peroxy-2-ethylhexanoate; diacyl
peroxides such as benzoyl peroxide, acetyl peroxide and lauroyl
peroxide; peroxyketals such as 2,2-d i(tert-butylperoxy)butane,
1,1-d i(tert-butylperoxy)cyclohexane and
1,1-bis(tert-butylperoxy)3,3,5-trimethylcyclohexane; and mixtures
thereof.
[0096] Examples of a suitable organic azo compound include
2,2'-azobisisobutyronitrile, dimethyl
2,2'-azobis(2-methylpropionate),
2,2'-azobis(2-methylbutyronitrile), 2,2'-azobis(2,4-d
imethylvaleronitrile), 4,4'-azobis(4-cyanopentanoic acid), and
mixtures thereof.
[0097] Examples of a suitable organotin compound are dimethyltin
chloride, dibutyltin chloride, and mixtures thereof.
[0098] The process carried out for preparing the ophthalmic lens
according to the invention, comprises the steps of:
[0099] a) providing monomers or oligomers from which the polymer
matrix can be prepared;
[0100] b) preparing nanoparticles encapsulating a light-absorbing
agent according to the method as defined in the second object of
the present invention, either in the form of a powder which is
dispersible within the monomers or oligomers or in the form of a
dispersion of nanoparticles in a liquid which is dispersible within
the monomers or oligomers;
[0101] c) providing a catalyst for initiating the polymerization of
said monomers or oligomers;
[0102] d) mixing the monomers or oligomers, the nanoparticles and
the catalyst so as to obtain a polymerizable liquid composition in
which nanoparticles are dispersed;
[0103] e) optionally depositing the polymerizable liquid
composition on a substrate;
[0104] f) curing the polymerizable liquid composition.
[0105] Preferably, the curing is a thermal curing.
[0106] As used herein, a coating that is said to be deposited on a
surface of a substrate is defined as a coating, which (i) is
positioned above the substrate, (ii) is not necessarily in contact
with the substrate, that is to say one or more intermediate layers
may be arranged between the substrate and the layer in question,
and (iii) does not necessarily completely cover the substrate.
[0107] A coating may be deposited or formed through various
methods, including wet processing, gaseous processing, and film
transfer.
[0108] According to a preferred embodiment, the polymerizable
liquid composition may be stirred until homogeneous and
subsequently degassed and/or filtered before curing.
[0109] According to a preferred embodiment, when nanoparticles are
provided in the form of a dispersion in a liquid, wherein the
dispersing liquid is dispersible within monomer or oligomer, in
particular, the dispersing liquid is the monomer or oligomer used
for generating the matrix according to the invention.
[0110] The polymerizable liquid composition described above may be
cast into a casting mold for forming a lens and polymerized by
heating at a temperature of from 40 to 130.degree. C., in
particular from 75 .degree. C. to 105 .degree. C. or in particular
from 100 .degree. C. to 150 .degree. C. or in particular from 45 to
95.degree. C. According to a preferred embodiment, the heating may
last for 5 to 24 hours, preferably 7 to 22 hours, more preferably
15 to 20 hours.
[0111] The casting mold may then be disassembled and the lens may
be cleaned with water, ethanol or isopropanol.
[0112] The ophthalmic lens may then be coated with one or more
functional coatings selected from the group consisting of an
anti-abrasion coating, an anti-reflection coating, an antifouling
coating, an antistatic coating, an anti-fog coating, a polarizing
coating, a tinted coating and a photochromic coating.
[0113] The light-absorbing agent LA that is contained in
nanoparticles dispersed in the composition is as already defined
above.
[0114] The ophthalmic lens according to the invention is a lens
which is designed to fit a spectacles frame so as to protect the
eye and/or correct the sight and can be an uncorrective (also
called plano or afocal lens) or corrective ophthalmic lens.
[0115] Corrective lens may be a unifocal, a bifocal, a trifocal or
a progressive lens.
[0116] The invention will now be described in more detail with the
following examples which are given for purely illustrative purposes
and which are not intended to limit the scope of the invention in
any manner.
EXAMPLES
[0117] Figures
[0118] FIG. 1a is a graph representing the absorption spectra of
nanoparticles obtained by the Stober method and measured before the
annealing step (0.03 wt. % of nanoparticles in CR-39.COPYRGT.)
comprising different concentration of methylene blue as a function
of Wavelength (nm). On this figure, the grey dotted line
corresponds to nanoparticles prepared with a methylene blue
solution at 1% w/w, the grey solid line corresponds to
nanoparticles prepared with a methylene blue solution at 2% w/w,
the black dotted line corresponds to nanoparticles prepared with a
methylene blue solution at 3% w/w, and the black solid line
corresponds to nanoparticles prepared with a methylene blue
solution at 4% w/w. The experimental protocol is detailed in
example 1 below.
[0119] FIG. 1b is a graph representing the absorption spectra of
nanoparticles from FIG. 1a, but measured after annealing at
180.degree. C. for 2 hours.
[0120] FIG. 2 gives the graphs representing the correlation of h*
(FIG. 2a) and C* (FIG. 2b) with silica nanoparticles prepared by
the Stober method with methylene blue solutions at 0.5, 1, 2, 3 or
4 wt %. On these graphs, h*, respectively C* (in absolute value) is
a function of methylene blue concentration (in % w/w).
[0121] FIG. 3 gives the results of the effects of the annealing
temperature (.degree. C.) of nanoparticles on the hue (h*) of clear
lenses comprising silica nanoparticles obtained by the Stober
method and prepared with a methylene blue solution at 2% w/w. On
this figure, diamonds correspond to 30 ppm of nanoparticles in
lenses, squares correspond to 70 ppm of nanoparticles in lenses and
triangles correspond to 150 ppm nanoparticles in lenses.
[0122] FIG. 4 gives the results of the effects of the annealing
temperature (.degree. C.) of nanoparticles on the hue (h*) of clear
lenses comprising silica nanoparticles obtained by the reverse
emulsion method and prepared with a 2% w/w solution of methylene
blue. On this figure, diamonds correspond to 80 ppm of
nanoparticles in lenses, squares correspond to 120 ppm of
nanoparticles in lenses and triangles correspond to 200 ppm of
nanoparticles in lenses.
[0123] FIG. 5 is the transmission spectra from lenses comprising 70
ppm of silica nanoparticles obtained by the Stober method, prepared
with a methylene blue solution at 2% w/w. and at different
annealing temperatures (lenses represented by squares in FIG. 3).
On this figure, the transmittance (% T) is a function of the
wavelength (in nm) and the grey solid curve corresponds to
annealing at 80.degree. C. for 2 hours, the curve in close-up lines
corresponds to annealing at 120.degree. C. for 2 hours and the
curve in spaced lines corresponds to annealing at 180.degree. C.
for 2 hours.
[0124] Materials
[0125] Chemicals used in the following examples are listed in Table
1 below:
TABLE-US-00001 TABLE 1 Component CAS Number Function CR-39 .RTM.
142-22-3 allyl monomer CR-39E .RTM. Proprietary allyl monomer (as
disclosed in U.S. Pat. No. 7,214,754) IPP 105-64-6 catalyst UV-9
000131-53-3 UV Absorber (benzophenone) Ammonium hydroxide 1336-21-6
Reagent solution (30%) Deionized Water (dH.sub.2O) -- Solvent
Tetraethyl orthosilicate 78-10-4 Silica precursor (TEOS) Methylene
blue 7720-79-3 Light absorbing agent Methanol 67-56-1 Solvent
Triton .RTM. X100 9002-93-1 Nonionic surfactant n-Hexanol 111-27-3
Solvent Cyclohexane 110-82-7 Solvent
[0126] Characterizations
[0127] Measure of the absorbance of nanoparticles: The absorbance
measurement protocol consists in dispersing 0.03 wt. % of dried
nanoparticles in CR-39, and measuring absorbance with a UV-Vis
spectrophotometer (Cary), with reference to a blank made of CR-39
without particles in a 2 mm thick cuvette.
[0128] Color of nanoparticles: Colorimetric parameters of the
nanoparticles of the invention are measured according to the
international colorimetric system CIE L*a*b*, i.e. calculated
between 380 and 780 nm, taking the standard illuminant D 65 at
angle of incidence 15.degree. and the observer into account (angle
of 10.degree.). 0.03% of dried particles are dispersed in CR-39 and
transmitted light through such material (in a 2 mm thick cuvette)
is measured (with comparison to blank). Colorimetric parameters of
this transmitted light are computed, yielding hue (h*) and chroma
(C*) of nanoparticles.
[0129] Color of lenses: Color of lenses are measured according to
the same principle as for nanoparticles, but on 2 mm thick lenses
at center. Transmitted light of lenses comprising nanoparticles is
measured and compared to the lens obtained with same polymerizable
composition but without particles. Colorimetric parameters of this
transmitted light are computed, yielding hue (h*) and chroma
(C*).
[0130] Size of nanoparticles: The size of the nanoparticles is
measured by standard Dynamic Light Scattering method. The technique
measures the time-dependent fluctuations in the intensity of
scattered light from a suspension of nanoparticles undergoing
random Brownian motion. Analysis of these intensity fluctuations
allows for the determination of the diffusion coefficients, which,
using the Stokes-Einstein relationship can be expressed as the
particle size.
Example 1
Preparation of Nanoparticles According to the Invention By the
Stober Method
[0131] Preparation:
[0132] In this example silica nanoparticles comprising methylene
blue as light absorbing agent were prepared by the Stober
method.
[0133] 24 mL of methanol, 6 mL of ammonium hydroxide solution
(30%), 0.4 mL of Methylene blue solutions (respectively at 1, 2, 3
and 4% w/w) and TEOS (0.2 mL) were mixed for 2 hours at a speed of
about 800 rpm. After reaction finished, the nanoparticles were
collected by centrifugation and washed with methanol. The
nanoparticles were then dried at room temperature until a constant
weight was attained. The nanoparticles were then annealed at 80,
120 or 180.degree. C. for 2 hours.
[0134] These nanoparticles can thereafter be used for the
manufacture of ophthalmic lenses after dispersion at 0.3 wt. % in
CR-39 (masterbatch).
[0135] Characterization
[0136] The effects of the concentration of methylene blue contained
in silica nanoparticles on their color have been determined by
measuring the absorbance of the nanoparticles measured before
performing annealing step (i.e. nanoparticules dried at ambient
temperature) and after performing the annealing step a 180.degree.
C. for 2 hours.
[0137] The absorption spectra of 0.03 wt. % nanoparticles in CR-39
as a function of Wavelength (nm), measured before performing the
annealing step, is represented on FIG. 1a annexed. On this figure,
the grey dotted line corresponds to nanoparticles prepared with a
methylene blue solution at 1% w/w, the grey solid line corresponds
to nanoparticles prepared with a methylene blue solution at 2% w/w,
the black dotted line corresponds to nanoparticles prepared with a
methylene blue solution at 3% w/w, and the black solid line
corresponds to nanoparticles prepared with a methylene blue
solution at 4% w/w.
[0138] As it can be seen on FIG. 1a, the variation of methylene
blue concentration in nanoparticles varied the color of
encapsulated material. Absorption peak of methylene blue show
different dimer/monomer ratio. At high concentration of methylene
blue solution, big dimer peak at 608 nm is dominant while monomer
peak at 670 nm arises after lowering concentration of methylene
blue solution.
[0139] FIG. 1b shows the absorption spectra of the same particles,
after annealing at 180.degree. C. for 2 hours. These results show
that the absorbance of monomeric form of methylene blue (above 650
nm) has almost disappeared. Methylene blue is present in form of
agglomerates predominantly after such annealing step.
[0140] FIG. 2 gives the graphs representing the correlation of h*
(FIG. 2a) and C* (FIG. 2b) with nanoparticles prepared with
methylene solutions at 0.5, 1, 2, 3 or 4 wt %. On these graphs, h*,
respectively C* (in absolute value) is a function of methylene blue
concentration (in % w/w).
[0141] These results show that C* increases with methylene blue
concentration, and more interesting h* roughly linearly increases
with methylene blue concentration too. These results demonstrate
that a change in light absorbing agent content in nanoparticle
mineral oxide matrix makes it possible to finely adjust the actual
hue of the light absorbing agent to reach optimum color, rather
than just increasing intensity (C*) of a color at a given hue. This
effect can be attributed to dimerization that occurs increasingly
when methylene blue is encapsulated in higher concentration in the
particles.
Example 2
Preparation of Nanoparticles According to the Invention By the
Reverse Emulsion Method
[0142] Preparation
[0143] In this example silica nanoparticles comprising methylene
blue as light absorbing agent were prepared by the reverse emulsion
method.
[0144] In 100 ml Duran bottle, 7.56 g of Triton X-100, 5.86 g of
n-hexanol, and 23.46 g of cyclohexane were mixed by magnetic
stirrer at a speed of 400 rpm for 15 min. After that, 1.6 ml
demineralized water was added dropwise, and stirring was continued
for a further 15 min. 0.32 ml of methylene blue solution (2% w/w)
were added dropwise. Stirring was continued for 15 min, 0.4 ml of
TEOS were then added dropwise and stirring continued for 15 min.
Last addition was ammonium hydroxide 30% w/w, dropwise 0.24 ml and
the mixture was stirred at a speed of 400 rpm for 24 h. Then 50 ml
of acetone was added and the nanoparticles were collected by
centrifugation, washed with acetone and dried at room temperature.
The nanoparticles were then annealed at 80, 120 or 180.degree. C.
for 2 hours.
[0145] These nanoparticles can thereafter be used for the
manufacture of ophthalmic lenses after dispersion at 0.3 wt. % in
CR-39 (masterbatch).
Example 3
Preparation of Ophthalmic Lenses Comprising Silica Nanoparticules
Comprising a Light Absorbing Agent
[0146] Masterbatches (MB) of nanoparticules (NP) prepared according
to example 1 with the methylene blue solution at 2% w/w and example
2 above (also obtained with a methylene blue solution at 2% w/w)
were used to prepare ophthalmic lenses.
[0147] Monomer Formulations
[0148] Different monomer formulations (MF) were prepared. Their
compositions (in wt. %) are detailed in Table 2 below:
TABLE-US-00002 TABLE 2 Annealing NP of NP of temp. Ex. 1 Ex. 2 MF
(.degree. C.) CR-39 CR-39E (MB) (MB) UV-9 IPP 1 80 94.03 2.00 1.00
-- 0.05 2.92 2 80 92.70 2.00 2.33 -- 0.05 2.92 3 80 90.03 2.00 5.00
-- 0.05 2.92 4 120 94.03 2.00 1.00 -- 0.05 2.92 5 120 92.70 2.00
2.33 -- 0.05 2.92 6 120 90.03 2.00 5.00 -- 0.05 2.92 7 180 94.03
2.00 1.00 -- 0.05 2.92 8 180 92.70 2.00 2.33 -- 0.05 2.92 9 180
90.03 2.00 5.00 -- 0.05 2.92 10 80 92.36 2.00 -- 2.67 0.05 2.92 11
80 91.03 2.00 -- 4.00 0.05 2.92 12 80 88.36 2.00 -- 6.67 0.05 2.92
13 120 92.36 2.00 -- 2.67 0.05 2.92 14 120 91.03 2.00 -- 4.00 0.05
2.92 15 120 88.36 2.00 -- 6.67 0.05 2.92 16 180 92.36 2.00 -- 2.67
0.05 2.92 17 180 91.03 2.00 -- 4.00 0.05 2.92 18 180 88.36 2.00 --
6.67 0.05 2.92
[0149] Each monomer formulation was prepared by weighing and mixing
the different ingredients in a beaker. CR-39, CR-39E and
masterbatch containing nanoparticles were first mixed. Once
homogeneous, UV9 was added and then the beaker content was mixed
again until full dissolution. Finally, IPP was added and the
mixture was stirred thoroughly, then degassed and filtered.
[0150] Lens Manufacturing
[0151] Each monomer formulation was used to prepare ophthalmic
lenses according to a casting and polymerization process.
[0152] Plano glass molds were filled with each monomer formulations
using a cleaned syringe, and the polymerization was carried out in
a regulated oven in which the temperature was gradually increased
from 45 to 85.degree. C. in 15 hours and maintained at 85.degree.
C. during 2 hours. The molds were then disassembled and the
resulting lenses had a 2 mm thickness at their center.
[0153] Characterization
[0154] FIG. 3 gives the results of the effects of the annealing
temperature (.degree. C.) of nanoparticles on the hue (h*) of clear
lenses comprising silica nanoparticles obtained by the Stober
method and prepared with a methylene blue solution at 2% w/w. On
this figure, diamonds correspond to 30 ppm of nanoparticles in
lenses (MF1, MF4 and MF7), squares correspond to 70 ppm of
nanoparticles in lenses (MF2, MF5 and MF8) and triangles correspond
to 150 ppm nanoparticles in lenses (MF3, MF6 and MF9).
[0155] These results show that increasing annealing temperature
leads to increasing in h*.
[0156] FIG. 4 gives the results of the effects of the annealing
temperature (.degree. C.) of nanoparticles on the hue (h*) of clear
lenses comprising silica nanoparticles obtained by the reverse
emulsion method and prepared with a 2% w/w solution of methylene
blue. On this figure, diamonds correspond to 80 ppm of
nanoparticles in lenses (MF10, MF13 and MF16), squares correspond
to 120 ppm of nanoparticles in lenses (MF11, MF14 and MF17) and
triangles correspond to 200 ppm of nanoparticles in lenses (MF12,
MF15 and MF18).
[0157] These results show that increasing annealing temperature
leads to increasing in h*.
[0158] FIG. 5 is the transmission spectra from lenses comprising 70
ppm of silica nanoparticles obtained by the Stober method, prepared
with a methylene blue solution at 2% w/w. and at different
annealing temperatures (lenses represented by squares in FIG. 3,
MF2, MF5 and MF8). On this figure, the transmittance (% T) is a
function of the wavelength (in nm) and the grey solid curve
corresponds to annealing at 80.degree. C. for 2 hours, the curve in
close-up lines corresponds to annealing at 120.degree. C. for 2
hours and the curve in spaced lines corresponds to annealing at
180.degree. C. for 2 hours.
[0159] These results show that adding nanoparticles obtained after
performing io the annealing step at a temperature of 80.degree. C.
brings the transmission downward.
[0160] Moreover, varying annealing temperature enhances changing in
absorption spectra which leads to change of color tones of
lenses.
[0161] This example illustrates that lenses comprising a light
absorbing agent encapsulated in a mineral oxide matrix can be
adjusted to get the optimum color. The color generated can be
modified by selecting a type of encapsulation method, adding
various amounts of light absorbing agent at synthesis steps and
varying the annealing temperature. The color is then stable during
the lens fabrication process.
* * * * *